The Department of Defense (DoD) has numerous sites that contain groundwater contaminated with 2,4,6-trinitrotoluene (TNT). The currently applied technologies for treating TNT contaminated waters are carbon adsorption and chemical oxidation. Carbon adsorption is a non-destructive technology, which could create future liability issues and is inefficient at relatively low TNT concentrations. On the other hand, application of chemical oxidation for the treatment of TNT contaminated water generates trinitrobenzene (TNB), a by-product of the incomplete oxidation of TNT. TNB is regulated as strictly as TNT. Additionally, over 70% of the reactor required treatment time for meeting target levels is due solely for TNB removal. This study evaluated the potential integration of zero-valent metallic species and advanced oxidation for the treatment of waters contaminated with TNT. The idea was to reduce treatment time, and thus, operational costs, when advanced oxidation is used as a stand-alone treatment technology by reducing TNT prior to oxidation. The use of zero-valent metals as the first treatment step transformed TNT into reduced organic compounds which were easily oxidized. The effectiveness of zinc, iron, nickel, copper, and tin as TNT reducing agents was evaluated. Zinc and iron were selected for further study based on their performance degrading TNT. Then, the reduction mechanism (pathway) and associated by-products of TNT reduction using zinc were examined using a zinc specimen manufactured by Sigma Corporation. Three amines were identified during reduction : 2-amino-4,6-dinitrotoluene, 4-amino-2,6-dinitrotoluene, and 2,4-diamino-toluene. Other intermediates were observed but not identified. Many of these reduction by-products adsorbed strongly onto the metal surface, significantly reducing the rate of TNT degradation during aging experiments. The aging of the metallic species was modeled using a power decay law parameter with the rate expression for TNT degradation. Corrosion promoters such as KCl addition, ozonation, and peroxone were evaluated as alternatives to reactivate zinc and iron to achieve steady TNT degradation. The addition of KCl performed significantly better than ozonation and peroxone. Furthermore, addition of KCl during the reduction step using iron or zinc generated organics that were successfully mineralized by ozonation or peroxone.

No description available.

Yes / This paper focuses on the dispute over river Cauvery in Southern India. Among the causes of river water disputes are contested property rights, difficulty in enforcing such rights, conflict of uses and a lack of willingness to compromise. A co-operative outcome in such cases depends on several factors: asymmetry of power in a triadic relationship between a federal government and two riparian states (one upstream and one downstream). Other factors influencing co-operation are the extent to which the claims of river waters can be elevated from those of immediate riparian peoples to those of an entire state; the dominance of a masculine paradigm towards 'taming' river waters using 'hard' investments rather than 'soft' and decentralised alternatives. On the basis of district level data, the importance of river Cauvery to the hydrology, economy and polity of the two contesting states is examined. This analysis helps us to appreciate why the two riparian state governments have limited room to manouvre. Drawing from two brief case studies of Murray Darling Basin and recent litigation in the USA, and other international experiences of river water treaties, the paper identifies various implications for the resolution of Cauvery and other river water disputes.

The microbial source tracking (MST) methods of antibiotic resistance analysis (ARA) and fluorometry (to detect optical brighteners in detergents) were used in the summers of 2004 and 2005 to determine the origins of fecal pollution at beaches with a past history of, or the potential for, high enterococci counts and posted advisories. At Hilton and Anderson beaches, ARA and fluorometry in the summer of 2004 detected substantial human-origin pollution in locations producing consistently high counts of Enterococcus spp. Investigations by municipal officials led to the fluorometric detection and subsequent repair of sewage infrastructure problems at both beaches. The success of these mitigation efforts was confirmed during the summer of 2005 using ARA and fluorometry, with the results cross-validated by pulsed-field gel electrophoresis (PFGE). Results at other beaches indicated that birds and/or wildlife were largely responsible for elevated enterococci levels during 2004 and 2005. The application of fluorometry proved difficult in opens waters due to high levels of dilution, but showed potential for use in storm drains. An additional study developed and tested a new library-based MST approach based on the pattern of DNA band lengths produced by the amplification of the 16S-23S rDNA intergenic spacer region, and subsequent digestion using the restriction endonuclease MboI. Initial results from small known-source libraries yielded high average rates of correct classification (ARCC). However, an increase in the library size was accompanied by a reduction in the ARCC of the library and the method was deemed unsuccessful, and unsuitable for field application. A final study focused on the potential for classification bias with disproportionate source category sizes using discriminant analysis (DA), logistic regression (LR), and k-nearest neighbor (K-NN) statistical classification algorithms. Findings indicated that DA was the most robust algorithm for use with source category imbalance when measuring both correct and incorrect classification rates. Conversely k-NN was identified as the most sensitive algorithm to imbalances with the greatest levels of distortion obtained from the highest k values. Conclusions of this project include: 1) application of a validation set, as well as a minimum detectable percentage to known-source libraries aids in accurately assessing the classification power of the library and reducing the false positive identification of contributing fecal sources; 2) the validation of MST results using multiple methods is recommended for field applications; 3) fluorometry displayed potential for detecting optical brighteners as indicators of sewage leaks in storm drains; 4) the digestion of the 16S-23S rDNA intergenic spacer region of Enterococcus spp. using MboI does not provided suitable discriminatory power for use as an MST method; and 5) DA was the least, and k-NN the most, sensitive algorithm to imbalances in the size of source categories in a known-source library. / Ph. D.

[pt] Ftalatos são os plastificantes mais utilizados industrialmente, estando disseminados em todos os ecossistemas do mundo. Como são compostos exclusivamente sintéticos, sua presença é indicativa da industrialização de uma região. Sua toxicidade é baixa, porém existem indícios de possíveis efeitos como interferentes endócrinos, especialmente no sistema reprodutor masculino. No Brasil, existem poucos estudos sobre a ocorrência e comportamento dos ftalatos no meio ambiente. Nesta tese foi estudada sua ocorrência em amostras de águas potáveis de diversos bairros das cidades do Rio de Janeiro e Niterói e do ecossistema da Baía de Guanabara (águas, sedimentos e mexilhões), a qual recebe inúmeros aportes industriais. Todas as amostras foram coletadas, extraídas em fase sólida e analisadas por cromatografia em fase gasosa, utilizando detecção por captura de elétrons. As da Baía foram amostradas nas estações seca e chuvosa, em diferentes anos. As extrações de todas as amostras obtiveram excelente repetibilidade e recuperações superiores a 76%. As águas potáveis do Rio de Janeiro e Niterói apresentaram teores de ftalatos em concentrações muito menores do que as informadas para cidades da Europa e Estados Unidos. Tais teores puderam ser correlacionados com as extensões das redes dos sistemas de abastecimento de ambas as cidades. Todas as amostras da Baía mostraram contaminações qualiquantitativas muito inferiores, quando comparadas a outros ambientes costeiros. O estudo do biomonitoramento ativo evidenciou a eficiência e rapidez da depuração dos ftalatos nos mexilhões mais contaminados do ecossistema da Baía de Guanabara. / [en] Phthalates are the most used plasticizers in industrial products, worldwide distributed in environments. Their presence is often used to indicate a region industrialization degree. Although their reported toxicity is low, phthalates are indicated for possible endocrine disrupting effects, specially in male reproductive system. In Brazil, there are few studies about the environmental occurrence and distribution of phthalates. This thesis studied the occurrence of those compounds in potable waters samples from residential areas of Rio de Janeiro and Niterói cities, and in samples from the ecosystem of Guanabara Bay (waters, sediments and mussels), which receives several industrial inputs. All the samples were collected, solid-phase extracted and the phthalate contents analyzed by gas chromatography with electron capture detection. The ones from the Bay were sampled during the dry and rainy seasons, in different years. All the extractions presented excellent repeatability and recoveries above 76%. The potable water samples from both cities presented phthalate values considerably lower than those reported for European and American cities. The results could be correlated with the water net distribution lengths for both cities. All results from the Bay ecosystem showed lower contamination when compared to other coastal environments. The controlled transplant proved quick and efficient phthalate depuration of contaminated organisms from Guanabara Bay.

Naphthenic acids (NA) are a highly complex mixture of aliphatic carboxylic acids that may contain multiple rings and unsaturated double bonds, and are a subset of the naphthenic acid fraction components (NAFC), which can contain heteroatoms, unsaturations, and aromatic structures. Mono-carboxylated NAs can be classically represented by CnH2n+zO2 where z is a negative integer representing the hydrogen deficiency. NAs and NAFCs are components of the acid extractable organics (AEO) frequently associated with increased toxicity and observed at elevated concentrations in oil sands process waters (OSPW). Numerous chromatographic and mass spectrometry techniques have recently emerged to probe the composition and concentrations of these components. This thesis reports the use of a capillary hollow fiber polydimethylsiloxane (PDMS) membrane mounted on a probe interface that can be immersed directly into an aqueous sample. A methanol acceptor phase passing through the lumen transports analyte to an electrospray ionization source and a triple quadrupole mass spectrometer. This technique, termed condensed phase membrane introduction mass spectrometry (CP-MIMS), allows for rapid screening of m/z profiles and on-line quantification of NAs in complex samples within minutes. This thesis reports parametric studies of several model carboxylic acids and a standard naphthenic acid mixture (Merichem) involving the effect of sample pH on membrane transport and acceptor phase pH on ionization enhancement. Several quantitative strategies are explored including the use of an internal standard in the acceptor phase to correct for ionization suppression and variations in instrument sensitivity, and the use of selected ion monitoring (SIM) experiments to increase analytical sensitivity and potentially target specific NA isomer classes for quantitation. Analytical performance measures such as the linear dynamic range (1-2300 ppb [NA]T as Merichem), sensitivity (~1 ppb [NA]T as Merichem detection limit), precision (~20 %RSD for replicates of a single OSPW) and accuracy are reported. Quantitative results for various OSPW samples in the ppb to ppm range are reported as equivalents of several surrogates, including 1-pyrenebutyric acid (PyBA), Merichem, and a large-volume extract of northern Alberta OSPWs. The variety of quantitation strategies allows results to be compared with several other published methods. CP-MIMS results for three mid-range northern Alberta OSPWs are compared to analysis by Environment Canada with an average -21% bias. Results for five archived OSPWs spanning a wider concentration are compared to data from AXYS Analytical, with an average -49% bias. Applications of CP-MIMS as an in-situ monitor of removal efficiencies of NAs on adsorbents and real-time mass profile changes are also presented, along with some interpretation of the resulting high-resolution kinetic data to obtain decay constants. Using the targeted SIM method, adsorption decay can be followed in real-time for various isomer classes within the Merichem mixture, and kinetic data extracted to obtain decay constants for each. CP-MIMS is also used to characterize adsorption behavior for two activated biochars, including % removals for various loadings of each when added to stirred Merichem solutions. Preliminary multi-loading experiments are conducted with one biochar, and the ability of CP-MIMS to characterize adsorbent behavior by constructing adsorption isotherm plots is demonstrated. / Graduate

Thesis (MScEng (Civil Engineering))--University of Stellenbosch, 2010. / ENGLISH ABSTRACT: This investigation focused on the marine components of large direct seawater intake and brine discharge systems for seawater desalination plants, with the main aim to provide an overall design approach for these components. Due to its complexity, an overall and systematic design approach, addressing all the components (feedwater requirements, plant technology, marine structures and environmental issues) is required to ensure an optimum design. A literature review was done on the various desalination technologies, the main components of a seawater desalination plant, as well as the physical, hydraulic, operational and environmental issues regarding seawater extraction facilities, marine pipelines and discharge structures (diffuser). In order to obtain practical input to the development of an overall design approach, information regarding the marine structures of ten of the largest existing seawater desalination plants throughout the world were obtained and compared with each other and the available technologies. By way of example, the recently designed marine components of a new seawater reverse osmosis desalination plant in Namibia were reviewed and, as part of this thesis, alternative conceptual concepts which will include two additional components (sump and brine reservoir) were designed. The alternative design was compared with the actual design in order to determine the feasibility of the alternative in terms of operation and cost and subsequently provide input to the overall design recommendations. Furthermore, from the literature review it seems that there are still significant uncertainties regarding the required performance of a brine (dense) outfall and this required more attention in terms of environmental and hydraulic performance. Based on the Namibian plant, the diffuser configuration was analysed in terms of its hydraulic and environmental performance and subsequently some general guidance with specific respect to a brine diffuser was developed, which in turn formed part of the overall design approach for the marine components. Finally, the design approach for seawater intake structures, brine outfalls and the connecting marine pipelines is provided in the form of flow diagrams. / AFRIKAANSE OPSOMMING: Hierdie ondersoek handel oor die mariene komponente van groot en direkte toevoer van seewater en die sout-uitvloeisisteme van ontsoutingsaanlegte van seewater. Die doel is om ‘n oorsigtelike ontwerpbenadering vir hierdie component te verskaf. As gevolg van die kompleksiteit, is ‘n oorsigtelike en sistimatiese benadering, wat al die komponente (vereistes vir toevoerwater, tehnologie by die aanleg, mariene omstandighede en omgewingsfaktore) in ag neem noodsaaklik om die beste ontwerp te verseker. ‘n Literêre oorsig is gedoen ten opsigte van die tegnologie van verskeie ontsoutingsmetodes, die hoofkomponente van ‘n seewater-ontsoutingsaanleg, asook die fisiese, hidrouliese, operasionele en omgewingskwessies rakende die fasiliteite om die seewater te onttrek, die mariene pyplyne en die strukture vir die afvloei. Ten einde die optimum ontwerp te ontwikkel, is inligting oor die tegnologie en strukture van tien van die grootste bestaande onsoutingsaanlegte in die wêreld bekom, bestudeer en vergelyk Hulle is met mekaar vergelyk, asook met beskikbare tegnologie. As ‘n voorbeeld is die nuut ontwerpte mariene komponente van die nuwe ontsoutingsaanleg in Namibië, waar ontsouting d.m.v. omgekeerde osmose gedoen word ondersoek en as deel van hierdie tesis, is ‘n alternatiewe konsep, wat twee bykomende komponente – ‘n opvangput en reservoir vir die afloop – ontwerp. Hierdie alternatiewe ontwerp is met die werklike aanleg vergelyk om die uitvoerbaarheid van die onderneming en die koste daaraan verbonde te toets. Dit is gebruik as aanbeveling vir die oorhoofse ontwerp. Uit die literêre oorsig blyk dit dar daar nog groot onsekerheid is oor die vereistes van die (digte) waterafloop en dat meer aandag aan die omgewings- en hidrouliese aspekte gegee moet word. Met die Namibiese aanleg as voorbeeld, is die struktuur van die spreiers t.o.v. hidrouliese werkverrigting en die omgewing ontleed. Voortspruitend daaruit is algemene riglyne vir ‘n spesifieke spreier vir afloopwater ontwikkel, wat op sy beurt weer deel vorm van die oorhoofse ontwerp vir mariene komponente. Laastens is die ontwerp vir die strukture vir seewater-invloei, die afloopwater en die mariene verbindingspyplyne as vloeidigramme aangetoon.

L'application de la Directive Cadre sur l'Eau et l'obligation de surveillance de la qualité d'eau pour la consommation humaine et les activités récréatives ou industrielles, telles que la production d'eau potable, entraînent une forte demande pour des systèmes d'évaluation et de suivi de la qualité de l'eau. Le projet de recherche MIGR'HYCAR (http://www.migrhycar.com) a donc été mis en place pour répondre à un besoin opérationnel et à un défaut d'outils d'aide à la décision adaptés face aux déversements d'hydrocarbures en eaux continentales (rivières, lacs et estuaires) qui représente plus de 50% des déversements accidentels en France. Au cours du projet de recherche MIGR'HYCAR, un modèle mathématique de dérive de nappe d'hydrocarbures, composé d'un modèle lagrangien couplé à un modèle eulérien, a été développé dans la plate-forme hydro-informatique TELEMAC (http://www.opentelemac.org). Le modèle lagrangien décrit le mouvement de la nappe en surface en considérant celle-ci comme un ensemble de particules. Ainsi le modèle développé est capable de modéliser les principaux phénomènes agissant sur une nappe d'hydrocarbures une fois celle-ci déversée : convection, diffusion, échouage, re-largage, étalement, évaporation, dissolution et volatilisation. Bien que le phénomène de dissolution ne concerne qu'un très faible volume d'hydrocarbures, ce processus peut avoir des conséquences importantes du point de vue de la toxicité. Afin de suivre l'évolution du pétrole dissous, un modèle eulérien de suivi de traceurs a été adopté. La quantité de traceur dépend directement de la masse dissoute des particules lagrangiennes. Cette approche permet le suivi des hydrocarbures dissous dans la colonne d'eau. Des cinétiques effectuées en laboratoire ont pour but la calibration du modèle numérique. En complément de cas tests issus de la littérature et de cas réels, des résultats expérimentaux issus d'expérimentations effectuées en canal d'essai doivent permettre de vérifier et valider la qualité des simulations numériques sur des situations où les conditions ne sont que partiellement contrôlées / The application of the European Water Framework Directive on water quality for human consumption and industrial activities creates a need for water quality assessment and monitoring systems. The MIGR'HYCAR research project (http://www.migrhycar.com) was initiated to provide decisional tools for risks connected to oil spills in continental waters (rivers, lakes and estuaries), which represent more than 50% of accidental spills in France. Within the framework of this project, a new numerical oil spill model has been developed, as part of the Telemac hydro-informatics system (see: (http://www.opentelemac.org), by combining Lagrangian and Eulerian methods. The Lagrangian model describes the transport of an oil spill near the free surface. The oil spill model enables to simulate the main processes driving oil plumes: advection, diffusion, oil beaching, oil re-floating, evaporation, dissolution, spreading and volatilization. Though generally considered as a minor process, dissolution is important from the point of view of toxicity. To model dissolved oil in water, an Eulerian advection-diffusion model is used. The fraction of dissolved oil is represented by a passive tracer. This approach is able to follow dissolved hydrocarbons in the water column. Laboratory experiments were conducted to characterise the numerous kinetics of the processes listed above. In addition, meso-scale dynamic experiments in artificial channels and test cases derived from the literature are used to validate the numerical model

Passage of the Volstead Act in 1920 expanded the mission of the U.S. Coast Guard. Law enforcement directives required officers to use "all necessary force" should a liquor smuggling vessel refuse the order to stop. On March 22, 1929, the Coast Guard Cutter Dexter sank the Canadian-flagged rum runner I'm Alone in the Gulf of Mexico, triggering an international incident that centered on "hot pursuit" and treaty jurisdiction. International encounters occurred frequently during Prohibition. The I'm Alone incident was the first sinking of a foreign flagged vessel that cost the life of a foreign national. The I'm Alone affair reflected the barriers any federal law enforcement agency faced in making Prohibition effective. The rum runner captain became a celebrity in Canada, while the Coast Guard was vilified. The Coast Guard amended boarding procedures after the incident cautioning officers about the possibility of accidental deaths.

[pt] Efluentes oleosos são gerados de muitas fontes, tais como: indústrias petroquímicas, refinarias, plataformas de petróleo, fabricação de maquinarias, e até mesmo, no transporte, distribuição e armazenagem de óleo. O óleo presente na forma de emulsão é difícil de separar. Para quebrar essas emulsões, geralmente, são usados tratamentos químicos, biológicos, eletroquímicos, ultrafiltração. O processo de eletrocoagulação-flotação se inicia com a dissolução do anodo produzindo espécies aquosas (monoméricas, poliméricas) e precipitadas, espécies que funcionam como coagulantes e floculantes. As mesmas causam a desestabilização das emulsões através de mecanismos como a neutralização de carga superficial, ponte interparticular e coagulação por varredura, formando flocos de gotículas de óleo. A dissolução do metal no anodo é acompanhada da geração do gás hidrogênio no catodo. As bolhas são aderidas aos flocos, carregando-os até a superfície, onde são separados do reator, porém, dependendo da densidade deles, poderiam sedimentar-se. Neste trabalho, é avaliada a remoção de óleo de uma emulsão sintético pelo processo de eletrocoagulação-flotação. Avaliou-se a influência dos principais parâmetros de operação na taxa de redução da demanda química de oxigênio (DQO): concentração inicial do óleo; densidade de corrente; separação entre eletrodos; pH da solução; concentração de eletrólito. O efluente sintético foi preparado a partir de óleo Shell Talpa 30 e Oleáto de sódio como surfatante. Foi adicionado NaCl para aumentar a condutividade da solução. O pH inicial da emulsão foi de 8,70. O potencial zeta nessas condições teve um valor médio de -75mV, valor este que indicou a estabilidade da emulsão. / [en] The separation of emulsions or colloidal particles from wastewater is a major concern for the petroleum, metal manufacturing, food, textile, paper and hydrometallurgy industries. The emulsion present is very stable due to the presence of surfactants, so conventional methods can not be applied and it is necessary to combine one or two treatment processes for highly effective purification. Several techniques have been applied to treat these types of oily wastewater, e.g.: chemical, biological and electrochemical destabilization, ultrafiltration. Electrocoagulation is initiated by the oxidation of sacrificial anodes. The metal ions released combine to the hydroxyl ions produced at the cathode to form the corresponding metal hydroxides and others species, which cause the destabilization of the contaminants or particulate suspensions and form flocs. The bubbles hydrogen gas capturing and floating the flocs formed and separating from the liquid surface by scraping or settling depending on density of the flocs. In this work, the electrocoagulation technique was studied in order to treat concentrated oil-water emulsions chemically stabilized. This study was mainly focused on the effects of operating parameters such as: initial pH, current density, reaction time, NaCl concentration, electrode distance and inlet concentration on the abatement rate of chemical oxygen demand (COD). The synthetic emulsion was prepared from Shell - Talpa 30 oil (3g.L-1) and sodium dodecyl sulfate (1.0 g.L-1), also was added NaCl (3g L-1) for increasing the conductivity of the emulsion. Under those conditions we had a pH value around 8.70 and a zeta potential around -70mV, showing a good stability of the emulsion.